Bromobenzene → HCID 54203413, compound

HRID 845156Notes

Reaction equation

HRID 845156 reaction equation
Br[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[Mg].[CH3:9][N:10]([CH3:22])[CH2:11][C:12]#[C:13][CH:14]([C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1)[OH:15].[Cl-].[NH4+]>C(OCC)C>[CH3:22][N:10]([CH3:9])[CH2:11][CH:12]=[C:13]([C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1)[CH:14]([C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1)[OH:15]

Participants

6

Reactant 4

HCID 7961BromobenzeneHCID 25517Ammonium ChlorideHCID 5462224MagnesiumHCID 13672830HCID 13672830, compound

Product 1

HCID 54203413HCID 54203413, compoundYield 27.6%

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent3×

Procedure

A solution of bromobenzene (24.8 g) in ethyl ether (120 cc) is added dropwise over approximately 1 hour to a suspension of magnesium turnings (3.85 g) in ethyl ether (100 cc). 4-Dimethylamino-1-phenyl-2-butyn-1-ol (10 g) in ethyl ether (30 cc) is added over approximately 15 minutes to the black solution obtained. The reaction mixture is then refluxed for 3 hours and 30 minutes, and then poured into a mixture of ice (400 g) and a saturated aqueous solution (200 cc) of ammonium chloride. The organic phase is separated; the aqueous phase is extracted with methylene chloride (2×200 cc); the organic phases are combined, dried over magnesium sulphate, filtered and concentrated to dryness under reduced pressure (2.7 kPa) at 40° C. The residue is purified by "flash" chromatography [eluent: methanol/ethyl acetate (60/40 by volume)], fractions 18 to 39 are combined and concentrated to dryness under reduced pressure (2.7 kPa) at 40° C. After the residue has been recrystallised from isopropyl ether, 4-dimethylamino-1,2-diphenyl-2-buten-1-ol (E) (3.9 g) is obtained in the form of white crystals melting at 113° C.

Workup

  1. customobtained
  2. temperatureThe reaction mixture is then refluxed for 3 hours and 30 minutes
  3. customThe organic phase is separated
  4. extractionthe aqueous phase is extracted with methylene chloride (2×200 cc)
  5. dry with materialdried over magnesium sulphate
  6. filtrationfiltered
  7. concentrationconcentrated to dryness under reduced pressure (2.7 kPa) at 40° C
  8. customThe residue is purified by "flash" chromatography [eluent: methanol/ethyl acetate (60/40 by volume)], fractions 18 to 39
  9. concentrationconcentrated to dryness under reduced pressure (2.7 kPa) at 40° C
  10. customAfter the residue has been recrystallised from isopropyl ether

Sources & evidence

ORD record
ord-347add163a2344c2886196447ec73815
Source dataset
uspto-grants-1988_07
Patent number
US04755599

Reaction notes

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